Sulfoaluminous clinker without iron and without free lime, its process of preparation and its use in white binders

ABSTRACT

The lightly colored sulfoaluminous clinker contains:  
     more than 55% by weight of calcium sulfoaluminate phase (C 4 A 3 S)  
     more than 10% by weight of belite phase (C 2 S)  
     less than 10% by weight of anhydrite (CS ) and contains practically no ferrite phase, nor a gehlenite phase (C 2 AS), nor free lime.  
     It is prepared by a process of roasting carried out at temperatures comprised between about 1250° C. and 1350° C.  
     It can be used for a wide range of applications by combining it with a source of calcium sulfate and/or Portland cement, to obtain binders having specific properties (color, setup time, mechanical strength, expansion or contraction . . . ).

[0001] The present invention relates to a new sulfoaluminous clinker, its process of preparation and its use in binders, in particular in binders that are lightly tinted, lightly colored or white.

[0002] Hydraulic binders (including cements) are mineral powders which react with water so as to form a malleable paste which hardens after several hours.

[0003] The terms “hydraulic binder” and “cement” are frequently confused. Generally speaking, the hydraulic binders are comprised of cements with mineral additives. The production of the cement consists in roasting a mixture, comprised of suitable materials, in a rotating kiln, at high temperature (higher than 1450° C.). The nodules obtained after roasting, called clinker nodules, are ground to a suitable fineness (or specific surface) so as to activate the affinity of the cement for water. The cement is thus a ground clinker, with possible mineral additions.

[0004] Cements are illustrated conventionally by two types, Portland cements and aluminous cements.

[0005] To facilitate explanation, the standard abbreviations used in the text that follows are as follows: C represents CaO {overscore (S)} represents SO₃ A represents Al₂O₃ H represents H₂O S represents Si₂O₂ T represents TiO₂ F represents Fe₂O₃

[0006] Cements of the Portland type are comprised by four principal phases, alite C₃S (40-70%), belite C₂S (up to 30%), tricalcium aluminate C₃A (2-15%) and ferrite C₄AF (up to 15%). Gypsum is conventionally added (up to 5%) during grinding the clinker.

[0007] Cements of the aluminous type cover a range of binders which includes monocalcium aluminate CA as the principal constituent. The other principal phases of this range of cements are the ferrite phase C₄AF, and the calcium dialuminate phase CA₂.

[0008] A new type of cement has been created in the past 70 years. It is characterized by one of its phases called calcium sulfoaluminate C₄A₃S (Klein phase). The other phases are generally C₂S, C₄AF, CA, CA₂, C₁₂A₇, CS and free lime. Calcium sulfoaluminate hydrates differently as a function of the other phases present in the binder (binder=cement+addition of active minerals):

[0009] if C₄A₃S is the only reactive hydraulic phase, the products of hydration are calcium monosulfoaluminate and aluminum hydroxide:

C₄A₃S+18H→C₄ASH₁₂+2AH₃  (1)

[0010] This reaction begins very slowly and the paste remains malleable for a fairly long period of time.

[0011] In the presence of gypsum (or other calcium sulfate phases) C₄A₃S gives place to ettringite as the lower ratio gypsum/sulfoaluminate is greater than 2, and gives ettringite and calcium monosulfoaluminate in contrary case:

2C₄A₃S+2CSH₂+52H→C₆AS₃H₃₂+C₄ASH₁₂+4AH₃  (2)

C₄A₃S+2CSH₂+34H→C₆AS₃H₃₂+2AH₃   (3)

[0012] Reactions (2) and (3) begin more rapidly than reaction (1), and after beginning, are fairly rapid. As a consequence, the C₄A₃S base cements in the presence of calcium sulfate are the cements that set up rapidly with a period of malleability of more than 30 minutes. Moreover, with an excess of gypsum (molar ratio of calcium sulfate/calcium sulfoaluminate>2), they increase in volume.

[0013] Mixtures of C₄A₃S and lime (calcium oxide) give place to a hydraugarnet phase (C₃AH₆) and to an Afm phase (C₃A.½CS.½CH.xH):

C₄A₃S+7CH+2xH→C₃AH₆+2(C₃A.½CS.½CH.xH)  (4)

[0014] Mixtures of C₄A₃S, lime and calcium sulfate hydrate very rapidly to form ettringite:

C₄A₃S+8CSH₂+6C+80H→3C₆AS₃H₃₂  (5)

[0015] Here again, properties of expansion can be obtained if lime and the calcium sulfate are in excess.

[0016] Reactions (4) and (5) are very rapid and lead very quickly to setting up (which is to say in several minutes) and give rise to cements that harden very rapidly. Lime can be present in the binder as a portion of the composition, or can be the result of the dissolution of another phase: the principal phase of Portland cement C₃S, once in contact with water, liberates calcium hydroxide (the hydrated form of lime) which in turn accelerates the formation of hydrates according to reactions (4) or (5).

[0017] As a result, the kinetics of hydration of C₄A₃S depend largely on the phases present in the binder. This leads to different applications according to whether it is desired to obtain rapid hardening, rapid setup and/or properties of expansion. Several examples are cited hereafter:

[0018] U.S. Pat. Nos. 3,251,701, 3,155,526, 4,419,136 and 3,857,714 disclose expanding binders produced from a clinker including the calcium sulfoaluminate content of the clinker which is mixed with other constituents (for example gypsum or Portland cement) so as produce ettringite (reaction (3) or (5)) with an excess of gypsum and/or lime. This clinker, containing not only C₄A₃S but also lime and anhydrite, has limited application because of the long setup time (reaction (1)), which is required for numerous applications, is impossible to obtain.

[0019] U.S. Pat. No. 3,860,433 discloses a very high strength cement, with rapid setup comprised by 20 to 40% C₄A₃S, 10 to 35% CS, the rest being essentially C₂S. Because the CS content is high, the crushed clinker hydrates according to reactions (2) or (3). Obtaining a binder with a long setup time, such as reaction (1) favors, is impossible.

[0020] Ferro- and sulfoaluminous clinkers developed by CBMA (China Building Materials Academy) are comprised principally of C₄A_(3S, C) ₂S and C₄AF (see Table 1). They are very useful for general applications and specific applications such as construction in winter, the production of subterranean structures, marine construction and applications for reinforced concrete resistant to corrosion. However, their C₄AF content is always greater than 3%. This gives them a dark color. It is thus not of interest to incorporate clinkers in binders that must remain lightly colored or pigmented, such as coatings. TABLE 1 Compositions of ferro- and sulfoaluminous clinkers of CBMA C₄A₃{overscore (S)} C₂S C₄AF Sulfoaluminous 50-70% 10-25% 3-10% Ferroaluminous 45-60% 10-20% 15-25% 

[0021] WO 90/15033 discloses a clinker roasted between 1000 and 1200° C., comprised with a high content of C₄A₃S, with a molar ratio A/F greater than 0.64. There thus exists a ferrite phase in this clinker. The roasting temperature being very low, free lime must be present in a substantial quantity in the clinker, which prevents its use for applications with long setup times.

[0022] The patent EP 0 181 739 also discloses a clinker having a high content of C₄A₃S, with less than 1% free lime. However, this clinker includes iron (ferrite phase) which gives it a dark color (see Table 7 hereafter), and other phases such as CA₂, CA and C₂AS in large quantities (of the order of 20%).

[0023] It will thus be seen that each calcium sulfoaluminate base cement is adapted for limited uses. The producer must thus give users a range of sulfoaluminous clinkers of different types to suit various desired uses (short or long setup time, expansion, rapid hardening, high strength . . . ).

[0024] A first object of the invention is thus to provide a unique sulfoaluminous clinker, which permits, by combining it with calcium sulfate and/or Portland cement in suitable proportions, obtaining binders having desirable properties, particularly as to contraction/expansion, setup time, hardening and mechanical strength.

[0025] Another object of the invention is to provide a sulfoaluminous clinker of light color, even substantially white, which is to say in which the iron oxides or the other colored oxides such as for example chromium oxide, manganese oxide, are practically absent.

[0026] These objects are achieved by the sulfoaluminous clinker according to the invention, including:

[0027] more than 55% by weight of calcium sulfoaluminate phase (C₄A₃S)

[0028] more than 10% by weight of belite phase (C₂S)

[0029] less than 10% by weight of anhydrite (CS) and including practically no ferrite phase, nor gehlenite phase (C₂AS), nor free lime.

[0030] With practically white clinker (see Table 7 hereafter), it is possible to produce very lightly colored binders, or more colored or darker binders, simply by adding a coloring agent, which is impossible with dark colored clinkers.

[0031] The clinker according to the invention containing practically no free lime, its use is not limited to applications in which rapid setup is necessary. Thus, in the presence of free lime, reactions (4) and (5) cannot be avoided. Thus reaction (1) is favored, which permits the cement to set up slowly, a property generally required in numerous applications.

[0032] A low anhydrite content (<10%) permits the user to select for example, between reaction (1) and reactions (2) and (3) or between reaction (4) and reaction (5) as the predominant reaction. Thus, the user can control the expansion or contraction phenomenon, which depends principally on the molar ratio calcium sulfate/calcium sulfoaluminate (CS/C₄A₃S).

[0033] Moreover, if the anhydrite content is more than 10%, reaction (1) is never predominant, and one can never obtain binders with a slow setup with this clinker.

[0034] A high content of C₄A₃S (>55% by weight) according to the invention enlarges the range of the properties of this clinker during its use in a binder. Thus, on the one hand the ratio CS/C₄A₃S can be adjusted more easily if the C₄A₃S content is high, which permits the user better control of the expansion/contraction phenomenon. On the other hand, standards have shown that the C₄A₃S content of the clinker must be greater than 55% to obtain binders (compounds of said clinker, of Portland cement, and/or of calcium sulfate) with very rapid setup and hardening properties according to reaction (5).

[0035] For example, a mixture of 30% of a sulfoaluminous clinker with 60% of Portland cement and 10% of gypsum does not give a very short setup time (less than 10 minutes) if the C₄A₃S content of the clinker is below 55%.

[0036] It has been seen that the presence of belite (C₂S) in the clinker is altogether beneficial. On the one hand, this phase traps the lime and it is thus easier to obtain a clinker without free lime when the mixture contains silica. On the other hand, belite hydrates very slowly and hence is responsible for long term high mechanical strength.

[0037] Preferably, the sulfoaluminous clinker according to the invention includes:

[0038] from about 55% to 72% by weight of calcium sulfoaluminate phase (C₄A₃S)

[0039] from about 10% to 20% by weight of belite phase (C₂S)

[0040] from about 2% to 9% by weight of anhydrite (CS).

[0041] Preferably, it includes less than 5% by weight of gehlenite phase (C₂AS). When this value is less than 5%, the gehlenite phase is practically not detectable by present methods of x-ray diffraction. Preferably, it includes the content of free lime less than 0.2%, preferably less than 0.15%, or even less than about 0.1% by weight, and an iron content (expressed as Fe₂O₃) less than 0.3%, preferably 0.25%, or even less than about 0.20% by weight.

[0042] To obtain the lightest color possible, the total content of colored oxides other than iron oxide, of the clinker is preferably less than 0.7%, preferably less than about 0.5% by weight (namely, in particular, a content less than 0.5%, preferably below 0.3% of TiO₂, less than 0.1% of MnO, less than 0.05% of Cr₂O₃. . . ).

[0043] The present invention also relates to a process for the preparation of said sulfoaluminous clinker.

[0044] The preparation of sulfoaluminous clinker including more than 55% of C₄A₃S and practically no free lime, and this from a mixture containing no Fe₂O₃, is not easy.

[0045] Thus, it would be desirable to increase the roasting temperature so as to combine all the lime in a reasonable time, but the belite phase risks decomposing to give gehlenite.

[0046] At lower temperatures, the decomposition of the sulfospurrite to form belite is facilitated by the presence of iron oxides, lowering the decomposition temperature of the sulfospurrite C₅S₂S to 1230° C. Thus iron facilitates roasting sulfoaluminous clinkers. But the presence of iron oxides in the clinker of the invention is precisely what the inventors have sought to avoid.

[0047] It has however been discovered that the sulfoaluminous clinker according to the invention could be prepared by a process comprising:

[0048] the mixture of starting materials, for example limestone, bauxite, sand and gypsum, in concentrations such that the following weight proportions of oxides will be respected:

[0049] 4≦S≦10

[0050] 34≦A≦49

[0051] 37≦C≦45

[0052] other oxides≦2

[0053] balanced to 100 being S

[0054] then roasting this mixture between about 1250 and 1350° C., for a time sufficiently long to combine all the lime, followed by rapid cooling of the mixture in a non-oxidizing atmosphere.

[0055] Preferably, the mixture will moreover show the following weight proportions in C, A and S oxides:

[0056] A≦1.33*S+41

[0057] A≦-2.33*S+62

[0058] C≦0.83*S+37

[0059] C≧3*S+13

[0060] C≧-0.81*A+72

[0061] C≦-0.6*A+67

[0062] It is essential that the roasting temperature be comprised between 1250 and 1350° C. Thus, below 1250° C. sulfospurrite C₅S₂S can form, which has very weak hydraulic properties. Above 1350° C. gehlenite C₂AS forms, which is not reactive with water. Between 1250 and 1350° C. belite forms as the principal silicate phase. Moreover, at a temperature greater than 1350° C., the sulfate is volatile in the form of SO₂ gas, which promotes the decomposition of the calcium sulfoaluminate phase, and which is a harmful gas whose emission into the environment must be limited.

[0063] The duration of roasting must be sufficiently long to combine all the lime and to obtain a clinker having less than 10% anhydrite. This duration depends on the cooking conditions, particularly the air flow rate in the kiln and the flame temperature, however a duration of 30 minutes to 1 hour is generally sufficient.

[0064] Roasting is followed by rapid cooling. Thus, it has been discovered that the conditions of quenching influence the coloration of the clinker according to the invention. Rapid cooling in a non-oxidizing atmosphere renders the clinker more faintly colored. Cooling can be carried out by water quenching, or under a nitrogen atmosphere.

[0065] The last step consists in grinding the clinker to the required fineness to activate its hydraulic properties. The more the clinker has a high specific purpose (measured by the Blaine method), the better is its reactivity from a hydraulic viewpoint. Preferably, the clinker is ground until a specific Blaine surface greater than about 3000 cm²/g is obtained, preferably greater than about 5000 cm²/g.

[0066] The present invention also relates to the use of the clinker according to the invention for the preparation of a binder by mixing said clinker with a material which is a source of calcium oxide (for example Portland cement) and/or with a source of calcium sulfate (for example gypsum). According to the proportions of these three components, the binders obtained can have different properties, for example:

[0067] the ground sulfoaluminous clinker according to the invention, alone, is a cement that is slow to set up and harden (at least 5 hours);

[0068] a binder comprising 75 to 90% of sulfoaluminous clinker according to the invention, and 25 to 10% by weight of a source of calcium sulfate, has a setup time less than or equal to three hours and permits preparing, according to the EN 196 standard, a mortar which has a resistance to compression after 28 days greater than or equal to about 50 MPa;

[0069] a binder comprising 20 to 40% (preferably about 30%) of sulfoaluminous clinker according to the invention, 50 to 70% (preferably about 60%) of Portland cement and 5 to 25% (preferably about 10%) of a source of calcium sulfate, has a setup time less than or equal to 10 minutes, and permits preparing, according to the EN 196 standard, a mortar which has high mechanical performance in a short time.

[0070] a binder comprising 55 to 90% (preferably about 60%) of sulfoaluminous clinker according to the invention, 5 to 30% (preferably about 20%) of Portland cement and 10 to 30% (preferably about 20%) of a source of calcium sulfate has a setup time comprised between about 30 minutes and one hour, and permits preparing, according to the EN 196 standard, a mortar having a resistance to compression at 5 hours greater than about 20 MPa.

[0071] Preferably, the source of calcium sulfate is gypsum.

[0072] Other properties of the binder, as well as other advantages of the invention, are presented in the following illustrative examples, in connection with FIG. 1 which shows the expansion/contraction behavior of a binder in a ternary diagram: Portland cement—sulfoaluminous clinker—gypsum.

EXAMPLES Example 1

[0073] Preparation of a sulfoaluminous clinker according to the invention and of binders based on this clinker.

[0074] A mixture constituted by limestone, sand, white alumina and gypsum, according to the composition given in Table 2, is roasted at 1300° C. for one hour. TABLE 2 Composition of the mixture White Limestone Sand alumina Gypsum Mixture % by 43.1 4.9 19.6 32.4 100 weight of the mixture Loss upon 43.43 0.14 0.63 21.39 23.10 firing SiO₂ 0.00 98.09 0.08 0.59 4.97 Al₂O₃ 0.06 0.61 98.65 0.05 32.1 Fe₂O₃ 0.04 0.06 0.09 0.01 0.05 TiO₂ 0.01 0.02 0.00 0.00 0.01 MnO 0.00 0.00 0.01 0.02 0.01 CaO 55.78 0.02 0.15 33.09 30.57 MgO 0.61 0.00 0.03 0.14 0.29 SO₃ 0.00 0.00 0.07 44.89 8.79 K₂O 0.01 0.42 0.00 0.00 0.03 Na₂O 0.00 0.02 0.35 0.00 0.10 P₂O₅ 0.00 0.01 0.00 0.00 0.00 SrO 0.00 0.01 0.00 0.08 0.01

[0075] X-ray diffraction analysis of the clinker shows the presence of C₄A3{overscore (S)}, C₂S, CS, CA, CA₂, residual quartz and corundum. No ferrite phase, nor gehlenite, nor free lime were detected. The chemical analyses show that the composition of the clinker obtained is:

[0076] C₄A₃S=66%

[0077] C₂S=15%

[0078] CS=3%

[0079] Residual phases=16% (CA, CA₂, quartz, corundum)

[0080] Different binders have been prepared with the above sulfoaluminous clinker, in mixture with gypsum and white Portland cement. Their setup times have been measured by texturometry on pastes and their mechanical performances have been determined on mortars prepared according to the EN 196 standard, namely with silica sand CEN of 0 to 2 mm, a mass ratio of water/binder of 0.5 and a mass ratio binder/sand of ⅓. The results are given in the following Table 3. TABLE 3 Composition and performance of the binders Binder no. 1 2 3 4 5 Composition % Sulfoaluminous 100 75 60 70 30 clinker Gypsum / 25 20 10 10 White / / 20 20 60 Portland cement Setup time Beginning 23 h 2 h 10 30 min 50 min 4 min End 23 h 15 3 h 60 min 110 min 6 min Resistance to compression (MPa) at 3 hours — — 4.7 — — at 5 hours — — 24 5.2 9 at 1 day — 26 — 37 18 at 7 days — 67 — — — at 28 days 50 74 57 45 54

[0081] There will be noted particularly the rapidity of setup of binder 5 without prejudice to a long-term high resistance to compression.

Example 2

[0082] This example has for its object to show the effect of the presence of belite compared to that of gehlenite on the long-term mechanical performance of the sulfoaluminous clinkers of the present invention.

[0083] The clinker of the present invention differs from the sulfoaluminous clinker described in the patent EP-B-0 181 739 by the nature of the principal silicate phase; EP-B-0 181 739 includes gehlenite C₂AS whilst the clinker of the invention includes more than 10% of belite (see Table 4). TABLE 4 Comparison of the mineralogical composition of clinkers according to the invention (Example 1) and according to EP-B-0 181 739 Clinker according Clinker according Constituents to the invention to EP-B-0 181 739 C₄A₃{overscore (S)} 66% 60% CA, CA₂, C₁₂A₇ 15% 14% C₂S (belite) 15% — C₂AS (gehlenite) (nd) 17% C{overscore (S)}  3% — C₄AF —  3% CT —  4% Others (Ca, Mg, K,  1%  2% Na,...)

[0084] To these two clinkers was added gypsum (10% by weight) so as to obtain a binder having a molar ratio of calcium sulfate/sulfoaluminate substantially equal to 2 (stoechiometric proportions according to reaction (3)).

[0085] The development of the resistance to compression of the two binders (measured on a mortar prepared according to the EN 196 standard) during the first month were compared (Table 5). TABLE 5 Comparison of the development of compressive strength Clinker according Clinker described Age to the invention in EP-B-0 181 739 1 day 28 MPa 38 MPa 7 days 65 MPa 57 MPa 28 days 74 MPa 58 MPa

[0086] It will be noted that the mechanical strength of the binder containing clinker according to EP-B-0 181 739 does not develop after 7 days whilst that of the corresponding binder of the present invention continues to increase, to give a resistance to compression greater by more than 25% at the end of four weeks.

Example 3

[0087] There is prepared a mixture of gypsum, white alumina, limestone and limestone containing silica. The composition of this mixture is given in Table 6. TABLE 6 Composition of the mixture Limestone containing Limestone silica White alumina Gypsum Mixture % by 17.8 29.6 30.3 29.3 weight of the mixture Loss 43.29 35.10 0.63 20.30 23.05 upon firing SiO₂ (S) 0.34 19.24 0.08 1.97 6.35 Al₂O₃ (A) 0.08 0.47 98.56 0.37 29.43 Fe₂O₃ (F) 0.11 0.15 0.09 0.11 0.12 TiO₂ 0.01 0.03 0.00 0.01 0.01 MnO 0.02 0.00 0.01 0.01 0.01 CaO (C) 55.89 44.83 0.15 33.11 30.9 MgO 0.20 0.21 0.03 1.38 0.41 SO₃ (S) 0.08 0.05 0.07 41.90 9.4 K₂O 0.00 0.04 0.00 0.05 0.02 Na₂O 0.00 0.01 0.35 0.03 0.11 P₂O₅ 0.00 0.02 0.00 0.01 0.01 SrO 0.02 0.08 0.00 0.60 0.16

[0088] This mixture thus includes weight proportions of the following oxides (%): S=8.25; A=38.26; F=0.16; C=40.17; S=12.22; others=0.95.

[0089] This mixture was roasted at 1300° C. for one-half hour. Then the clinker was ground to a Blaine specific surface equal to 5000 cm²/g.

[0090] X-ray diffraction of the clinker shows that it is comprised of calcium sulfoaluminate, belite, anhydrite and calcium aluminate phases (CA, CA₂). The presence of uncombined alumina is also observed. Neither free limestone nor ferrite phase were detected. The content of C₄A₃S, C₂S, and CS is:

[0091] C₄A₃S=57%

[0092] C₂S=18%

[0093] CS=8%

[0094] Residual phases=17%

[0095] The whiteness index of the specimen is measured, according to the CIE 1931 standard under illuminant C (near natural light) at an angle of 45°. The color characteristics are given in the L-a-b system and are compared to those of a white Portland cement and to those of a sulfoaluminous clinker containing iron (see Table 7). The value L quantifies the luminance of the specimen, whilst a and b describe the color. Thus, the studied specimens are the whiter as L is nearer to 100 and as a and b are near to zero. TABLE 7 Color characteristics of the cements Sulfoaluminous clinker Sulfoaluminous according to clinker White EP-B-0 181 739 according to Portland (containing the invention cement iron) L 96.22 93.65 78.1 a −1.21 −2.54 0.1 b 2.05 4.33 15.4

Example 4

[0096] Preparation of other clinkers according to the invention.

[0097] Three clinkers were prepared from gypsum, white alumina, and two different limestones: one containing silica and the other not containing it.

[0098] The mixture was roasted at 1300° C. for 30 minutes. Then each clinker was ground to a Blaine specific surface equal to 5000 cm²/g. Their mineralogical compositions (content of belite, anhydrite and calcium sulfoaluminate) are given in Table 8. TABLE 8 Composition of obtained clinkers Residual Clinker C₂S (%) C{overscore (S)} (%) C₄A₃{overscore (S)} (%) phases 1 11.5 4 70 15.5 2 12.5 7 61.5 19 3 17.5 7.5 57.5 17.5

[0099] From these clinkers, two types of binders have been prepared:

[0100] Type A binder: binder with rapid setup and hardening comprised b 60% Portland cement, 30% sulfoaluminous clinker according to the invention and 10% gypsum;

[0101] Type B binder: binder constituted by each clinker and by gypsum in stoechiometric proportions according to reaction (3), which hardens slowly.

[0102] For each binder A, have been determined the setup times (initial and final) and the compressive strength after 5 hours of hydration, and for each binder B the setup times and the compressive strength at 28 days (for mortars prepared according to the EN 196 standard). The results are given in Tables 9 and 10. TABLE 9 Type A binders No. of Compressive clinker Setup time Setup time strength at Binder used Initial Final 5 hours A1 1    5 min. 30 s  7 min. 5.5 MPa   A2 2 8 min. 10 min. 6 MPa A3 3 7 min. 10 min. 5 MPa

[0103] TABLE 10 Type B binders Compressive No. of Initial setup strength at Binder clinker used time 28 days B2 2 110 min. 67 MPa B3 3 110 min. 63 MPa

[0104] Thus, with each clinker, it is possible to produce a binder with rapid setup and hardening, as well as a binder with slow setup having long-term high compression strength. By varying the content of Portland cement and calcium sulfate of the binder, the setup time can be fixed as well as the hardening time to respond to the requirements of any desired application. This clinker is thus somewhat a “universal” clinker.

Example 5

[0105] The sulfoaluminous clinker of Example 1 was used to prepare five different binders so as to test their properties of contraction and expansion. The compositions of the binders are given in Table 11. TABLE 11 Composition of the binders (% by weight) Binder Binder Binder Binder Binder 1 2 3 4 5 Portland 60%  0% 20% 20% 35% cement Sulfoaluminous 30% 73% 55% 40% 65% clinker Gypsum 10% 27% 25% 40%  0%

[0106] The hydrated mortars, prepared according to the EN 196 standard (weight ratio of binder/sand=0.33 and water/binder=0.5) have been held in a controlled atmosphere (50% relative humidity at 20° C.) to measure the contraction or immersed in water at 20° C. to measure their expansion. The results are collected in Tables 12 and 13 hereafter. TABLE 12 Measurement of expansion (μm/m). Duration of treatment Binder 1 Binder 2 Binder 3 Binder 4 Binder 5 2 days 40 60 −30 620 −70 7 days 60 50 −10 760 10 28 days  −20 20 10 820

[0107] TABLE 13 Measurement of contraction (μm/m) Duration of treatment Binder 1 Binder 2 Binder 3 Binder 4 Binder 5 2 days 60 160 245 105 270 7 days 250 350 315 150 500 28 days  390 510 380 240

[0108] As can be seen in FIG. 1, the binders having low properties of contraction/expansion are compositions near line D in the ternary system Portland cement-sulfoaluminous clinker-gypsum.

[0109] In zone 1, the corresponding binders have properties of expansion (compare binder 4). On the contrary, in zone 2, there is observed substantial contraction (compare binder 5).

[0110] The ternary diagram of FIG. 1 thus permits:

[0111] knowing the composition of a binder, which is to say its properties as to gypsum, sulfoaluminous clinker according to the invention, and Portland cement, to foretell its contraction or expansion behavior;

[0112] or conversely, as a function of specifications imposing limit values of contraction or expansion, to select the appropriate composition of gypsum, sulfoaluminous clinker according to the invention and Portland cement of the binder to be used. 

1. Sulfoaluminous clinker containing: more than 55% by weight of calcium sulfoaluminate phase (C₄A₃S) from 10 to 20% by weight of belite phase (C₂S) less than 10% by weight of anhydrite (CS) less than 5% by weight of gehlenite phase (C₂AS), a free lime content less than about 0.2% by weight, and an iron content (expressed as Fe₂O₃) less than about 0.3% by weight.
 2. Sulfoaluminous clinker according to claim 1, characterized in that it contains: from about 55% to 72% by weight of calcium sulphoaluminate phase (C₄A₃S) from about 2% to 9% by weight of anhydrite (CS).
 3. Clinker according to one of claims 1 or 2, characterized in that the total content of colored oxides other than iron oxide is less than about 0.7% by weight.
 4. Process for the preparation of the clinker according to any one of claims 1 to 3, comprising mixing first materials in compositions such that the following weight proportions of oxides will be respected: 4≦S≦10 34≦A≦49 37≦C≦45 other oxides≦2 balance to 100 being S then roasting this mixture between about 1250° and 1350° C., for a time sufficiently long to combine all the lime, followed by rapid cooling of the mixture in a non-oxidizing atmosphere.
 5. Process according to claim 4, characterized in that the mixture respects moreover the following weight proportions in C, A and S oxides: A≦1.33*S+41 A≦−2.33*S+62 C≦0.83*S+37 C≧3*S+13 C≧−0.81*A+72 C≧−0.6*A+67
 6. Process according to claim 4 or 5, characterized in that the cooling is carried out by quenching in water.
 7. Process according to claim 4 or 5, characterized in that the cooling is carried out under a nitrogen atmosphere.
 8. Process according to one of claims 4 to 7, characterized in that the clinker is then ground to obtain a Blaine specific surface greater than about 3000 cm²/g.
 9. Process according to claim 8, characterized in that the clinker is ground to obtain a Blaine specific surface greater than about 5000 cm²/g.
 10. The use of the clinker according to one of claims 1 to 3 or obtained by the process according to one of claims 4 to 9, for the preparation of a binder by mixing said clinker with a material that is a source of calcium oxide and/or a source of calcium sulfate.
 11. The use according to claim 10, for the preparation of a binder by mixing said clinker with Portland cement and/or a source of calcium sulfate.
 12. Binder comprising from 75 to 90% of sulfoaluminous clinker according to one of claims 1 to 3 or obtained by the process according to one of claims 4 to 9, and 25 to 10% by weight of a source of calcium sulfate, having a setup time less than or equal to three hours and permitting preparing, according to the EN 196 standard, a mortar which has a compressive strength at 28 days greater than or equal to about 50 MPa.
 13. Binder comprising from 20 to 40% of sulfoaluminous clinker according to one of claims 1 to 3, or obtained by the process according to one of claims 4 to 9, from 50 to 70% of Portland cement and from 5 to 25% of a source of calcium sulfate, having a setup time less than or equal to 10 minutes.
 14. Binder according to claim 13 comprising about 30% of sulfoaluminous clinker, about 60% of Portland cement and about 10% of a source of calcium sulfate.
 15. Binder comprising 55 to 90% of sulfoaluminous clinker according to one of claims 1 to 3, or obtained by the process according to one of claims 4 to 9, from 5 to 30% of Portland cement and from 10 to 30% of a source of calcium sulfate, having a setup time comprised between about 30 minutes and 1 hour, and permitting preparing, according to the EN 196 standard, a mortar which has a compressive strength at 5 hours greater than about 20 MPa.
 16. Binder according to claim 15, comprising about 60% of sulfoaluminous clinker, about 20% of Portland cement and about 20% of a source of calcium sulfate.
 17. Binder according to one of claims 11 to 16, characterized in that the source of calcium sulfate is gypsum. 